CN108273546A - A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene - Google Patents

A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene Download PDF

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CN108273546A
CN108273546A CN201810152397.4A CN201810152397A CN108273546A CN 108273546 A CN108273546 A CN 108273546A CN 201810152397 A CN201810152397 A CN 201810152397A CN 108273546 A CN108273546 A CN 108273546A
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zsm
catalytic cracking
perrhenic acid
naphtha
tetrabutyl ammonium
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CN108273546B (en
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彭杰
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Beijing Suihuo Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7846—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, step is：Include the following steps：It uses hydrothermal synthesis method to prepare 5 composite molecular screens of EU 1/ZSM first, γ Al is then added2O3, it is uniformly mixed, using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, obtains naphtha catalytic cracking catalyst for preparing propene.It uses naphtha catalytic cracking catalyst for preparing propene prepared by the present invention that can be produced with catalytic pyrolysis naphtha and obtains more propylene products.In the preferred embodiment of the present invention, 94% or more of the pyrolysis product total weight that the amount of obtained ethylene, propylene and butylene is, and productivity of propylene is high.

Description

A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene
Technical field
The invention belongs to naphtha catalytic cracking technical fields, and in particular to a kind of naphtha catalytic cracking propylene catalysis The preparation method of agent.
Background technology
Since the new century, worldwide petrochemical raw material and petroleum chemicals demand will sustainable growth, it is former as petrochemical industry basis Material ethylene, propylene demand will continue to increase, and conventional steam pyrolysis technology production capacity cannot meet rapid growth Propylene demand, and conventional tubular stove steam thermal cracking is the process of a large amount of consumption energy, and process conditions are harsh.Naphtha is catalyzed Cracking is compared with steam thermal cracking, and the process reaction temperature is 50 DEG C ~ 200 DEG C about lower than Standard cleavage reaction, therefore, than commonly steaming Vapour thermal cracking less energy consumption, cracking furnace pipe inner wall coking rate reduces, and so as to extend the operation cycle, increases the boiler tube service life.One oxygen Changing carbon emission can also reduce, and product structure can be adjusted flexibly.Compared with traditional steam pyrolysis technology, this new technology can Increase the total recovery of ethylene and propylene, producing feed naphtha used in identical quantity ethylene can be reduced, and production cost of ethylene is substantially Degree reduces.Conventional ethylene cracking be mainly raw material by steam heat producing ethylene by cracking and propylene using naphtha, wherein being heated Cracking reaction mechanism limits, and general propylene/ethylene ratio is maximum limit about 0.65, is higher than this ratio, total olefin will Decline.This process needs to consume a large amount of high-quality feed naphtha, is the process of a high energy consumption.The third of current 66% ~ 70% Alkene is produced with steam pyrolysis technology.
CN101279881A discloses a kind of method of the production of catalytic pyrolysis naphtha ethylene and propylene, with C4~C16Hydrocarbon Naphtha is raw material, before contact with catalyst after raw material hydrocarbon vaporization, elder generation with to reacting inert gas mixing, wherein indifferent gas The molar ratio of body and naphtha is more than 0 and to be less than or equal to 5.0:1, it is 580 DEG C ~ 750 DEG C in reaction temperature, is reacted in terms of gauge pressure Pressure is more than 0 and to be less than or equal to 0.5MPa, and weight space velocity is 0.5 ~ 3h-1, water/naphtha weight ratio is 0 ~ 5:Under conditions of 1, Material mixed gas generates ethylene and propylene with catalyst haptoreaction, and wherein used catalyst is selected from ZSM-5/ mordenite coexistings At least one of molecular sieve, ZSM-5/ beta zeolite coexistings molecular sieve or ZSM-5/Y zeolite coexisting molecular sieves.
CN1958731A discloses a kind of method of catalytic pyrolysis producing olefinic hydrocarbons, wherein will include naphtha, light diesel fuel and The cracking petroleum hydrocarbon raw material of hydrogenation tail oil, by the catalyst bed of concatenated two fillings different catalysts a and b up and down, into Row catalytic cracking reaction, obtains olefine in low carbon number.
Although the above prior art can obtain propylene or light olefin, the yield of propylene is still relatively low.Accordingly, it would be desirable to be able to Naphtha catalytic cracking is enough set to produce the higher method of propene yield.
Invention content
The present invention the technical issues of actually solving is：The yield for solving propylene in existing naphtha cracking process is lower Problem, the key technology means of use are to load perrhenic acid and tetrabutyl ammonium perrhenate in EU-1/ZSM-5 composite molecular screens to carry Height produces naphtha pyrolysis the selectivity of propylene.The present invention provides a kind of preparation of naphtha catalytic cracking catalyst for preparing propene Method, the method can obtain the propylene of higher yields.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, includes the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein Si/Al molar ratios are 50~300；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 1h~3h, 520 DEG C~560 DEG C roasting 4h~6h is dried in type at 100 DEG C~120 DEG C；
(3) using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, first by perrhenic acid and the high rhenium of the tetrabutyl Sour ammonium is dissolved in 60 DEG C~80 DEG C of water, then with obtained perrhenic acid and the tetrabutyl ammonium perrhenate aqueous solution dipping EU-1/ ZSM-5 molecular sieve 5h~12h；Then dry 6h~10h, obtains naphtha catalytic cracking system third at a temperature of 100 DEG C~300 DEG C Alkene catalyst, wherein EU-1/ZSM-5 composite molecular screens：γ-Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:15 ~30:0.3~2:0.5~1.
Preferably, crystallization temperature is 100 DEG C~150 DEG C in the step (1), crystallization time 30h~60h；Calcination temperature 400 DEG C~650 DEG C, roasting time 3h~8h.
Preferably, Si/Al molar ratios are 200 in the step (1).
Preferably, perrhenic acid and tetrabutyl ammonium perrhenate are dissolved in 65 DEG C of water in the step (3).
Preferably, EU-1/ZSM-5 composite molecular screens in the step (3)：γ-Al2O3：Perrhenic acid：Tetrabutyl perrhenic acid Ammonium mass ratio is 100:25:1.2:0.6.
Advantageous effect：
It uses naphtha catalytic cracking catalyst for preparing propene prepared by the present invention that can produce with catalytic pyrolysis naphtha to obtain more Propylene product.In the preferred embodiment of the present invention, the pyrolysis product that the amount of obtained ethylene, propylene and butylene is is total 94% or more of weight, and productivity of propylene is high.
Specific implementation mode
The present invention is further described in detail below by specific embodiment, but not limited to this.
Embodiment 1
A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, includes the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein crystallization temperature be 150 DEG C, crystallization time 40h, 650 DEG C, roasting time 3h of calcination temperature, Si/Al molar ratios are 150 in composite molecular screen；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 1h, 560 DEG C of roasting 4h is dried in type at 110 DEG C；
(3) using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, first by perrhenic acid and the high rhenium of the tetrabutyl Sour ammonium is dissolved in 80 DEG C of water, then with obtained perrhenic acid and the tetrabutyl ammonium perrhenate aqueous solution dipping EU-1/ZSM-5 molecules Sieve 5h；Then dry 10h at a temperature of 100 DEG C, obtains naphtha catalytic cracking catalyst for preparing propene, and wherein EU-1/ZSM-5 is multiple Close molecular sieve：γ-Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:20:0.6:1.
Embodiment 2
A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, includes the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein crystallization temperature be 100 DEG C, crystallization time 30h, 400 DEG C, roasting time 5h of calcination temperature, Si/Al molar ratios are 50 in composite molecular screen；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 2h, 520 DEG C of roasting 6h is dried in type at 120 DEG C；
(3) using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, first by perrhenic acid and the high rhenium of the tetrabutyl Sour ammonium is dissolved in 60 DEG C of water, then with obtained perrhenic acid and the tetrabutyl ammonium perrhenate aqueous solution dipping EU-1/ZSM-5 molecules Sieve 8h；Then dry 6h at a temperature of 300 DEG C, obtains naphtha catalytic cracking catalyst for preparing propene, and wherein EU-1/ZSM-5 is multiple Close molecular sieve：γ-Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:30:2:0.7.
Embodiment 3
A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, includes the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein crystallization temperature be 140 DEG C, crystallization time 60h, 500 DEG C, roasting time 8h of calcination temperature, Si/Al molar ratios are 300 in composite molecular screen；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 3h, 550 DEG C of roasting 5h is dried in type at 100 DEG C；
(3) using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, first by perrhenic acid and the high rhenium of the tetrabutyl Sour ammonium is dissolved in 70 DEG C of water, then with obtained perrhenic acid and the tetrabutyl ammonium perrhenate aqueous solution dipping EU-1/ZSM-5 molecules Sieve 12h；Then dry 7h at a temperature of 250 DEG C, obtains naphtha catalytic cracking catalyst for preparing propene, and wherein EU-1/ZSM-5 is multiple Close molecular sieve：γ-Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:15: 0.3:0.5.
Embodiment 4
A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, includes the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein crystallization temperature be 120 DEG C, crystallization time 40h, 550 DEG C, roasting time 5h of calcination temperature, Si/Al molar ratios are 200 in composite molecular screen；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 2h, 540 DEG C of roasting 5h is dried in type at 120 DEG C；
(3) using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, first by perrhenic acid and the high rhenium of the tetrabutyl Sour ammonium is dissolved in 65 DEG C of water, then with obtained perrhenic acid and the tetrabutyl ammonium perrhenate aqueous solution dipping EU-1/ZSM-5 molecules Sieve 10h；Then dry 8h at a temperature of 200 DEG C, obtains naphtha catalytic cracking catalyst for preparing propene, and wherein EU-1/ZSM-5 is multiple Close molecular sieve：γ-Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:25:1.2:0.6.
Comparative example 1
A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, includes the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein crystallization temperature be 120 DEG C, crystallization time 40h, 550 DEG C, roasting time 5h of calcination temperature, Si/Al molar ratios are 200 in composite molecular screen；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 2h, 540 DEG C of roasting 5h is dried in type at 120 DEG C；
(3) perrhenic acid is loaded using infusion process after molding, be dissolved in perrhenic acid in 65 DEG C of water first, then with obtained height Rehenic acid aqueous solution impregnates EU-1/ZSM-5 molecular sieves 10h；Then dry 8h at a temperature of 200 DEG C, obtains naphtha catalytic cracking Catalyst for preparing propene, wherein EU-1/ZSM-5 composite molecular screens：γ-Al2O3：Perrhenic acid mass ratio is 100:25:1.2.
Naphtha catalytic cracking catalyst for preparing propene prepared by above-described embodiment and comparative example is catalyzed applied to naphtha Cracking alkene processed, using C5~C10 naphthas as raw material, using fixed bed reaction technique, reaction temperature is 600 DEG C, reaction pressure 0.1MPa, naphtha mass space velocity are 1.2h-1, water oil volume than 0.8, by gas chromatography analysis method surveyed by gas-phase product property It is fixed.Yield and selectivity are calculated by the following formula to obtain：
Yield=(purpose product production quantity/reaction-ure feeding amount) × 100%
Selectivity=(purpose product production quantity/reactant inversion quantity) × 100%
Test result is as follows shown in table：
Project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1
C3/C2 5.2 5.6 5.8 6.3 3.5
C2+C3Yield, % 87.23 87.56 89.14 90.20 79.16
C2~C4Selectivity, % 98.24 96.51 97.15 99.22 94.23
The naphtha catalytic cracking catalyst for preparing propene prepared by embodiment, which is can be seen that, from above-mentioned experimental result is applied to stone brain The C of high yield can be obtained in oily producing olefin hydrocarbon by catalytic pyrolysis2~C4Olefin product, C2+C3Yield reach 87% or more, C3/C2It reaches To 5 or more, illustrate that the catalyst prepared prepares propylene to naphtha catalytic cracking and has very high selectivity.Wherein comparative example 1 In relative to tetrabutyl ammonium perrhenate is not added in embodiment 4, although comparative example C2~C4Olefin product reaches 94%, but C2+C3 Yield there was only 79%, C3/C2Only 3.5, C2+C3Yield and C3/C2Well below embodiment 4, illustrate that four are added in catalyst Butyl ammonium perrhenate prepares propylene to naphtha catalytic cracking has very high selectivity.Naphtha catalysis prepared by the present invention Cracking catalyst for preparing propene, there is moderate acid distribution, stable structure, the catalyst can not only improve the yield of propylene, Further increasing improves its stability on the basis of catalyst activity, moreover it is possible to reduce reaction temperature, save energy consumption.

Claims (5)

1. a kind of preparation method of naphtha catalytic cracking catalyst for preparing propene, it is characterised in that include the following steps：
(1) it uses hydrothermal synthesis method to prepare EU-1/ZSM-5 composite molecular screens, weighs suitable TPAOH and TPABr, distilled water, It stirs evenly, adds EU-1 molecular sieves, stir evenly, be eventually adding Ludox, synthesis reactor is packed into after stirring, pass through Crystallization, be filtered, washed, dry, roasting, ammonium exchange system obtains Hydrogen EU-1/ZSM-5 composite molecular screens, wherein Si/Al molar ratios are 50~300；
(2) γ-Al are added2O3, be uniformly mixed, be added appropriate sesbania powder and a concentration of 10% dilute nitric acid solution kneading extrusion at 1h~3h, 520 DEG C~560 DEG C roasting 4h~6h is dried in type at 100 DEG C~120 DEG C；
(3) using infusion process load perrhenic acid and tetrabutyl ammonium perrhenate after molding, first by perrhenic acid and the high rhenium of the tetrabutyl Sour ammonium is dissolved in 60 DEG C~80 DEG C of water, then with obtained perrhenic acid and the tetrabutyl ammonium perrhenate aqueous solution dipping EU-1/ ZSM-5 molecular sieve 5h~12h；Then dry 6h~10h, obtains naphtha catalytic cracking system third at a temperature of 100 DEG C~300 DEG C Alkene catalyst, wherein EU-1/ZSM-5 composite molecular screens：γ-Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:15 ~30:0.3~2:0.5~1.
2. according to claim 1, it is characterised in that crystallization temperature is 100 DEG C~150 DEG C, crystallization time 30h~60h； 400 DEG C~650 DEG C of calcination temperature, roasting time 3h~8h.
3. according to claim 1, it is characterised in that Si/Al molar ratios are 200 in the step (1).
4. according to claim 1, it is characterised in that be dissolved in perrhenic acid and tetrabutyl ammonium perrhenate in the step (3) In 65 DEG C of water.
5. according to claim 1, it is characterised in that EU-1/ZSM-5 composite molecular screens in the step (3)：γ- Al2O3：Perrhenic acid：Tetrabutyl ammonium perrhenate mass ratio is 100:25:1.2:0.6.
CN201810152397.4A 2018-02-14 2018-02-14 Preparation method of catalyst for preparing propylene by catalytic cracking of naphtha Expired - Fee Related CN108273546B (en)

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Publication number Priority date Publication date Assignee Title
CN112299433A (en) * 2019-07-29 2021-02-02 中国石油天然气股份有限公司 Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application
CN112299433B (en) * 2019-07-29 2022-06-03 中国石油天然气股份有限公司 Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application

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